Among scanned probe microscopies (SPMs), electrochemical microscopies, such as scanning electrochemical microscopy (SECM), have attracted considerable attention as a means of mapping the function, as well as topography of a wide range of surfaces and interfaces. Amperometric SECM generally employs a working electrode tip, as part of an electrochemical cell, in which an electrolyte solution bathes the entire sample of interest. While SECM has provided significant advances, there can be issues from the long exposure of the sample to solution (corrosion, passivation fouling etc.) and the SECM tip design and positioning methods presently used means that measurements of surface reactivity are made neither as directly nor precisely as desired in some instances; there are limits to the spatial resolution attainable and the type of information that can be obtained.